Polyvinyl halide compositions



Patented Aug. 28, 1951 UNI ED STATES PATENT OFFICE POLYVhIYL HALIDECOMPOSITIONS corporation of Ohio No Drawing. Original applicationJanuary 18,

1945, Serial No. 573,461.

Divided and this application November 15, 1947, Serial No. 786,314

8 Claims. 1

This invention relates to polyvinyl halide compositions, and moreparticularly, to new and improved plasticized polyvinyl halidecompositions.

The present application is a division ofcopending application Serial No.573,461, iiled January 18, 1945, now abandoned.

The term a polymerized vinyl halide" rei'ers to polymeric compositionsthat are wholly or primarily a polyvinyl halide. This includescompositions consisting substantially of a vinyl chloride polymer andcompositions in which vinyl acetate or vinylidene chloride has beencopolymerized with vinyl chloride in the manufacture of the polymer.

It is well known to those skilled in the art that polyvinyl halides arevery difllcult to plasticize because many plasticizers which aresuitable for plasticizing other types of materials, such ascelluloseacetate, nitrocellulose and ethyl cellulose, are unsuitable forplasticizing polyvinyl halide polymers. It is not possible to predictthat a plasticizer for a cellulose derivative such as cellulose acetatewill also be a suitable plasticizer for polyvinyl halide polymers. Agreat many ood plasticizers for cellulose derivatives are poorplasticizers for polyvinyl halides.

Both the chemical structur and the molecula weight of a givenplasticizer appear to influence its relative compatibility withcellulose derivatives and polyvinyl halides. Thus, the monobenzoylhenzoic acid esters of glycerine and ethylene glycol which contain freehydroxyl groups are not suitable plasticizers for polyvinyl halidepolymers.

-The incompatibility of the plasticizer with the I ll polyvinyl halidepolymer causes the plasticizer to suitable as plasticizers for po yvinylhalide films are usuallysolvents for varnish and lacquer, the

polyvinyl halide products containing them may damage varnished andlacquered surfaces where z I Another object of the invention is toprepare polyvinyl halide compositions containing plasticlzers which donot sweat out to the suriace of polyvinyl halide films and moldedobjects formed from the compoations. Another object of the invention isto provide newand useful plasticized polyvinyl halide compositions fromreadily available raw materials.

Still a further object of the invention is to prepare new and usefulpolyvinyl chloride emulsions containing plasticizers and characterizedby the ability to deposit clear fi ms from the emulsion system upon airdrying. Other objects will appear hereinafter.

In accordance with the invention, it has been found that new andimprovedresults are obtained in plasticizing polymerized vinyl halidepolymers with esters in which the carboxylic acid radical of ano-benzoyl benzoic acid is esterifled either by.

a polyhydric alcohol or by an alcohol ether in such a way that theresultant compound contains no free hydroxy groups. Where theplasticizer is pounds and the polyvinyl halide compositions containingthem are very stable against loss of this incompatibility and consequentsweating occurs. Another disadvantage of some plasticizers is that theheating of a composition con- 4:5 taining the plasticizer may cause lossof the plasticizer and thereby produce an unstable polyvinyl halidecomposition.

One of the objects of the present invention is to provide polyvinylhalide compositions plasticized only small amounts of the plasticizerare lost upon aging of a dim containing it.

the plasticizer due to heating. It was not predictable that such highmolecular weight compounds would be suitable plasticizers [or polyvinylhalide compositions because, in general, increasing the molecular weightof a plasticizer results in decreased compatibility of the plasticizerwith a polyvinyl halide polymer. As will be understood, however,chemical structure, as well as molecular weight, are important factorsin determining the suitability of a plasticizer for plasticizing aparticu'ar type of composition. Thus, if one of the benzoyl benzoic acidgroups in such a poly-ester is substituted by an alkyl radical of thesame molecular weight the compatibility of the resultant material as aplasticizer for polyvinyl halide compositions is greatly decreased. Thisshows that chemical structure is a more important factor than molecularweight These plasticizers are, "therefore, relatively high molecularweight com- EXAMPLE 1:

A solution was prepared by mixing together 750 parts of methyl ethylketone, 250 parts of toluene, heating to boiling. and adding 40 parts ofa polyvinyl chloride polymer (Vinylite QYNA) The mixture was stirred andheated until solution was eilected during which a part of the sol ventwas evaporated. Additional solvent was added until the total solutionweight was 1000 parts. I

One part of triethylene glycol di(o-(p-toluyl) benzoate) was mixed withparts of the aforementioned polyvinyl chloride solution until solutionwas eifected, and the resultant solution was then poured into a cleansurface, viz., a tin vessel, in order to produce a layer about 1%" to/8" thick. The resultant layer was then" heated to 200 degrees F. forabout 20 to minutes, and the condition of the film was noted aftercooling. The film was not cloudy, had not receded from the edge of thevessel, and did not show any evidence of sweating out even afterstanding a few days. It was pliable but not sticky. Also, it wascompletely colorless and continued to remain so while retaining all ofits original pliability.

EXAMPLE If batch was obtained. The material was then cooled and strippedfrom the mill. The plasticizer was found to be compatible.

EXAMPLEIII A polyvinyl chloride emulsion was prepared by preparing:

A3.8 parts of a casein emulsion in 23.6 parts of water;

B-13.4 parts triethylene glycol dim-(ptiialluyl) benzoate) in 9.4 partsdehydrated pine o C49.8 parts of a'commercial polyvinyl chlorideemulsion containing 50.4% solids.

A was put into a mixing pump and B added intermittently. The resultantmixture was then mixed with a spatula into 49.8 parts of C. The finalemulsion contained 39.2% solids. This product when baked or air driedgave a perfectly clear film of good chemical stability and toughness. a

In a similar manner the invention may be practiced with the followingplasticizers:

Table A Character- Ester Mics Dlethylene glycol diSo(p-toluyl) benzoate)Semi-Solid,

(From diethylene g ycol and o-(p-toluyl) benzoic acid) Dig ropyleneglycol di(op-toluyl) benzoate) rom dlpropylene glycol and o-(p-toluyl)benzoic aci Glyceryl tri(0-(p-toluyl) benzoate) (From lycerinc ando-(p-toluyl) benzoic acid) G yceryl tri(o-benzoyl benzoate) (Fromglycerine and o-benzoyl benzoic acid) Glycol di(o-(p-toluyl) benzoat'e)(From ethylene glycol and o-(p-toluyl) benzoic acid) Ethyl carbitolo-benzoyl benzoate (From ethyl carbitol and o-benzoyl benzoic acid)Butyl cellosolve o-benzoyl benzoate (From butyl cellosolve and o-benzoylbenzoic acid) Nonaethylene glycol di(o-(p-toluyl) benzoatc) (Fromnonaethylene glycol and o-(p-toluyl) benzoic acid) Triethylene glycoldi(o-benzoyl benzoate) (Eromtriethylene glycol and o-benzoyl benzolcacid) Butyl cellosolve o-(p-toluyl) benzoate From ethylene glycolmono-butyl ether an o-(ptoluyl) benzoic acid) Butyl carbitolo-(p-toluyl) benzoate (From diethylene glycol mono-butyl ether and o-(p-toluyl) benzoic acid) Ethyl cerbitol o-(ptoluyl) benzoate (Fromdiethylene glycol mono-ethyl ether and o- (p-toluyl) benzoic acid)Liquid.

Semi-Solid.

Liquid.

(k) Do.

Semi-Solid.

l Vis. Z5 (Gardner-Holdt), specific gravity 1.09.

The expression an o-benzoyl benzoic acid is used herein to describegenerically o-benoyl benzoic acid, o-(p-toluyl) benzoic acid and relatedcompounds. v

The o-benzoyl benzoic acid portion of the ester molecule may have one ormore of the hydrogen pose of the invention include ethylene, propyleneand butylene glycols; di-, tri-, tetra-, penta-, hexa-, hepta-, octa-,and nona-ethylene glycols; di-, tri-, and tetrapropylene glycols; mixedethylene-propylene glycols; methyl, ethyl and butyl ethers of diethyleneglycol; methyl. ethyl, butyl, benzyl and phenyl ethers of ethyleneglycol; glycerine; and homologues thereof.

In preparing plasticizers for the purpose of the invention, it ispreferable to esterify an o-benzoyl benzoic acid in either one of twoways, namely, (1) without a solvent or (2) in the presence of a solvent.The non-solvent method (method No. 1) is preferably employed where theesterifying agent is ethylene glycol or other low boiling water solublealcohol or alcohol ether. The solvent method is preferably used with thehigher boiling types of esterifying agents, such as, for example,triethylene "glycol. Any organic solvent which is inert to the reactingmaterials, and which is a solvent for one or both of the reactingmaterials; may be used although especially good results have beenobtained with toluene. I

The usual esteriflcation catalysts may be used but are not necessary. Ingeneral, the presence of a catalyst causes discoloration andnecessitates washing- In most cases, at temperatures around 380 degreesF. to 400 degrees F., the

stantially to completion in the absence of a catalyst. Highertemperatures usually cause discoloration and lower temperatures decreasethe esterification rate. The addition of toluene 01' other waterremoving solvents at intervals during the reaction serves to control thetemperature and to maintain a rapid reflux rate.

In general, the plasticizers derived from glycols and glycerine aresolid, semi-solid, or liquid, whereas those derived from alkyl ethers ofalkylene giycols and other ether-alcohols are liquids. They are veryhigh boiling compounds, insoluble in water, and have specific gravitiesof approximately 1.1. They are also characterized by low vapor pressuresat room temperatures (e. g., 75 degrees F.).

The quantity of ester of the type herein described required toplasticize a polymerized vinyl halide may vary rather widely dependingupon the specific substances and the result desired. For example, asmall amount, say 12% of ester, might be added to increase the toughnessof the polymeric compound. Larger amounts, preferably 5% and upwards byweight of the ester can be used up to the limit of compatibility, i. e.,the point where the product is no longer tackfree and sweating outoccurs. With polyvinyl chloride, good results are still obtained evenwith as much as 60% of ester, based upon the total weight of thecomposition.

Those plasticizers are especially adaptable to polyvinyl chloride resinsand other related plastics such as vinylidene chloride polymers of theSaran F type. Polyvinyl chloride films plasticized with these compoundshave excellent toughness and strength. With certain other plasticizersit is possible to deposit clear films by bake ing under the influence ofheat, but air dried films with the same plasticizers are not clear andcontinuous. With the esters of this invention, however, it is possibleto deposit emulsions which will air dry to clear continuous films. Thisopens up a new field for such polymers, since their use has beenretarded by the high cost of solvents fcr vinyl chloride polymers and bythe low concentration of film-forming material that can be dissolved.Hence, plasticizers making it possible to lay clear air dried films arean important contribution to the coating industry.

Coating compositions prepared in accordance with the invention andcontaining plasticizers of the type described herein may also containother customary ingredients such as pigments. dispersing agents andother auxiliary materials added for a specific purpose.

Having thus described the invention, what I claim as new and desire tosecure by Letters Patent of the United States is:

1. A composition of matter comprising a polymerized vinyl halide and aplasticizer which is an ester cf an o-benzoyl benzoic acid having thecarboxylic acid radical of the o-benzoyl benzplc acid esterified by anamount of an organic hydroxy compound selected from the classcolisisting of glycerol, alkylene glycols and ethers of said glycolssuflicient to esterify said acid without leaving unreacted. hydroxylgroups.

2. A film-forming composition comprising as the primary film-formingmaterial a polymerized vinyl chloride, and containing plasticizingamounts of an ester in which the carboxylic acid radical of an o-benzoylbenzoic acid is esterifled by an amount of an organic hydroxy compoundselected from the class consisting of glycerol, alkylene glycols andethers of said glycols: suflicient to esterify said acid without leavingunreacted hydroxyl groups.

3. A film-forming composition comprising a polymerized vinyl chloride asthe primary filmlorming material. and containing plasticizing amounts ofa di-ester of an alkylene glycol in which the two hydroxyl groups areesterified with an o-benzoyl benzoic acid.

4. A film-forming composition comprising a polymerized vinyl chlorideand plasticizing amounts of triethylene glycol di(o-lp-toluyl)benzoate).

5. A polymerized vinyl chloride oil and water emulsion containing as aplasticizer a quantity of a di-ester of an alkylene glycol in which thetwo hydroxyl groups of the alkylene glycol are eterified with ano-benzoyl benzoic acid, said emulsion forming clear air dried films whenapplied as a coating composition.

6. A composition of matter comprising a polymer made from a monomericmaterial consisting essentially of vinyl chloride and as a plasticizertherefor the o-(p-toluyl) benzoic acid ester of diethylene glycolmonobutyl ether.

7. A film-forming composition comprising an emulsion consistingessentially of a casein in water and oil emulsion and a polymerizedvinyl chloride in water emulsion containing an ester of an o-benzoylbenzoic acid having the carboxylic acid radical of the o-benzoyl benzoicacid csterified by an amount of an organic; hydroxy compound from theclass consisting of glycerol, alkylene glycols and ethers of saidglycols sufficient to esterify said acid without leaving unreactedhydroxyl groups.

8. A film-forming composition comprising an emulsion consistingessentially of a casein in water and oil emulsion and a polymerizedvinyl chloride in water emulsion containing triethylene glycoldi-(o(ptoluyl) benzoate).

JAMES V. HUNN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,036,271 Hahn Apr. 7. 19362,372,947 Gresham Apr. 3, 1945

7. A FILM-FORMING COMPOSITION COMPRISING AN EMULSION CONSISTINGESSENTIALLY OF A CASEIN IN WATER AND OIL EMULSION AND A POLYMERIZEDVINYL CHLORIDE IN WATER EMULSION CONTAINING AN ESTER OF AN O-BENZOYLBENOZIC ACID HAVING THE CARBOXYLIC ACID RADICAL OF THE O-BENZOYL BENZOICACID ESTERIFIED BY AN AMOUNT OF AN ORGANIC HYDROXY COMPOUND FROM THECLASS CONSISTING OF GLYCEROL, ALKYLENE GLYCOLS AND ESTERS OF SAIDGLYCOLS SUFFICIENT TO ESTERIFY SAID ACID WITHOUT LEAVING UNREACTEDHYDROXYL GROUPS.